<p>Vitrimers belong to a class of polymeric materials capable of bond exchange reactions, showing great promise for environmental protection and sustainable development. However, studies on the coupling mechanism between the bond exchange kinetics and segmental dynamics near the glass transition temperature (<i>T</i>_g) remain scarce. Herein, we employed molecular dynamics simulations to investigate the dynamic heterogeneity of the segment motion and bond exchange in vitrimers. The simulation results revealed that the bond exchange energy barrier exerts a much stronger influence on the bond exchange kinetics than on the segmental dynamics. At lower temperatures, slower segmental relaxation further constraind the bond exchange rate. Additionally, increasing the bond exchange energy barrier markedly enhanced the dynamic heterogeneity of segment motion. A close correlation was observed between heterogeneity and bond exchange. This study elucidated the coupling mechanism between bond exchange and segmental dynamics at the molecular scale, thereby providing a theoretical basis for designing vitrimer materials with tunable dynamic properties.</p>